An Overview of Industrial Processes for the Production
of Olefins – C4 Hydrocarbons
Michael Bender[1]
Abstract
The survey describes industrial processes for the
production of light olefins emphasizing on C4 hy-
drocarbons. Value chains in the petrochemical and
the oil refining industry are strongly interrelated
with regards to olefin production. An account is
Keywords: Butadiene, Butylene, Hydrocarbons, Industrial processes, Olefins
Received: June 25, 2014; accepted: June 30, 2014
DOI: 10.1002/cben.201400016
1 Production and Consumption
of Butenes
Today, light olefins are produced by a number of processes in
the petrochemical and oil refining industry. Worldwide, a vol-
ume of 1 billion t of various hydrocarbon feedstock is used to
generate approx. 400 million t of light olefins per year. The
residual product volume (ca. 600 million t) is composed of
higher hydrocarbons, mainly of gasoline fractions (Fig. 1).
Approx. 60 % of the global feedstock volume is processed in
fluid-catalytic cracking (FCC) units in oil refineries. The re-
mainder of 40 % is used in steam cracking in ethylene plants.
Ethylene is almost exclusively generated in these plants, in sim-
ilar amounts from steam cracking of naphtha and gas oil and
of ethane and liquefied petroleum gas (LPG), respectively.
At present, increasing volumes of ethylene are also produced
by modified FCC processes, such as deep catalytic cracking
(DCC). In difference to ethylene, only half of the global propyl-
ene volume is generated by steam cracking, mostly of naphtha
and gas oil. The other half of the global propylene production
rests on conventional FCC units in oil refineries. About a tenth
of the global propylene is generated in dedicated processes, in
particular by olefin metathesis of 2-butene and ethylene, as well
as by propane dehydrogenation (PDH).
In difference to the former two light olefins, C4 hydrocar-
bons are mainly generated in FCC units as a by-product of gas-
oline production. Only a quarter of the global C4 hydrocarbon
volume stems from steam cracking of naphtha and gas oil.
Marginal volumes of C4 olefins are currently produced by bu-
tane dehydrogenation (BDH).
While volume growth rates of the light olefins are close to
the growth of the gross domestic product (GDP) at 4 to 5 % a–1,
the world gasoline demand is expected to grow by only 1 % a–1.
www.ChemBioEngRev.de ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
given on the production and the consumption
volumes of the various C4 hydrocarbons on a global
basis, including an outlook for alternative, petro-
chemical and bio-based processes for the produc-
tion of C4 olefins.
Thus, growth in global feedstock for olefin production can be
expected to be slower by 1 to 2 % than olefin growth rates, i.e.,
at approx. 3 % a–1.
Four different C4 olefins are industrially relevant, namely
1-butene, 2-butene, isobutene, and butadiene. These olefins are
generated and further processed jointly with n- and isobutane
in a complex network of industrial processes. In some cases the
C4 olefins are purified and used in substance, but in the major-
ity of all cases C4 olefins are further processed when contained
in C4 fractions, the so-called raffinates (Fig. 2).
Steam cracking of naphtha and gas oil yields a butadiene-
rich C4 fraction, the so-called crude C4. Butadiene is produced
in substance from this product stream by extraction, yielding a
by-product stream of the remaining C4 components, the so-
called raffinate 1. Raffinate 1 is rich in isobutene, but also con-
tains significant amounts of the n-butene isomers. In some
cases the valuable butadiene is not recovered, but crude C4 is
processed by selective hydrogenation of the butadiene, yielding
additional volumes of n-butenes in the raffinate 1 product
stream.
Steam cracking of ethane or LPG yields only small amounts
of C4 olefins that cannot be recovered economically. These
volumes are often hydrogenated fully to butanes, which are re-
cycled back into the cracker furnaces as so-called co-crack. In-
stead, 1-butene that is required, e.g., as a co-monomer for the
manufacturing of linear low density polyethylene (lldPE), can
be produced from ethylene by dimerization.
—————
[1]
Dr. Michael Bender
BASF SE, Ludwigshafen, Germany.
E-Mail: michael.bender@basf.com
ChemBioEng Rev 2014, 1, No. 4, 136–147 136
 a) processes for olefin production yield C4 hydrocarbons in differ-
ent ratios. Steam cracking almost exclusively yields C4 olefins,
Dehydrogenation Steam cracking, while FCC units are operated such that the total C4 olefin con-
2% Ethane & LPG tent and the isobutane content of the raffinate 1 stream are in a
11%
stoichiometric one-to-one balance. This ratio is required to fur-
ther process these components into alkylate gasoline. n-Butane
Steam cracking, does not react under the alkylation process conditions. Other
liquid feed ratios of C4 hydrocarbons are obtained, e.g., in the upcoming
28% dehydrogenation processes (Tab. 1).
Fluid-catalytic Beyond butadiene production, raffinates are further proc-
cracking Total HCx feed to Olefins
59% 1,015 Mmto / +3 % p.a. essed to a number of different products. Raffinate 1 is used to
manufacture methyl tert-butyl ether (MTBE) and ethyl tert-bu-
tyl ether (ETBE) by acid-catalyzed, selective etherification of
b) isobutene with methanol and ethanol, respectively. Both MTBE
Fluid / Deep and ETBE are large-scale products used as important additives
Steam cracking,
Catalytic Cracking Ethane & LPG to the gasoline pool.
5% 38% Alternatively, C4 olefins can be catalytically converted with
isobutane in raffinates yielding alkylate gasoline, another im-
portant additive to the gasoline pool. Additional isobutene
volumes can be generated from n-butenes by acid-catalyzed
skeletal isomerization. As an example for this process type
Steam cracking, CDTech’s ISOMPlus process can be named. ISOMPlus operates
Naphtha / GO Ethylene a ferrierite catalyst at 340 to 440 C to generate isobutene from
57% 156 Mmto / +4.5% p.a. n-butenes by rearranging the molecular carbon skeleton [13].
Isobutene can be recovered in substance by acid-catalyzed
c) cleavage of MTBE or iso- and tert-butanol, respectively. Isobu-
tene is consumed in substance, e.g., for the production of poly-
Propane Other (XTP, etc.) isobutene (PIB).
Dehydrogenation 1%
5% 1-Butene can be isomerized by acid catalysis or by hydroiso-
Steam cracking,
merization to 2-butene. N-olefins can be produced in substance
Ethane & LPG
Metathesis 8% by catalytic distillation. They are used for some specific, mostly
5% Steam cracking, chemical production processes.
naphtha & GO
Fluid / Deep 42%
Catalytic Cracking Propylene
2 The Growing Market for Butenes
39% 100 Mmto / +5 % p.a.
Worldwide, approx. 30 million t of isobutylene are generated
per year, mainly in oil refineries, where it is directly processed
d) into MTBE, ETBE, and alkylate gasoline. Much smaller vol-
Steam cracking, Steam cracking, umes are chemically processed into elastomers such as PIB or
Ethane & LPG liquid feed into chemical intermediates such as methacrylic acid and its
4% 22% derivatives (Fig. 3).
Delayed The growth rate of global isobutylene volumes is largely driv-
Coking Butane en by growth of its two main products. Historically, alkylate
1% Dehydrogenation gasoline and MTBE volumes have grown rapidly by approx.
4% 4 % a–1. MTBE volumes but were stagnant in the recent past
Fluid-catalytic due to the MTBE ban in the U.S. and other regions. Mean-
cracking* Crude C4” yield, total while, ETBE has started to substitute these volumes and growth
69% 132 Mmto / +4 % p.a. of the two ethers combined is expected to continue at historic
pace, supporting an expected growth rate of approx. 4 % a–1 for
Figure 1. Global volumes by process type: Total hydrocarbon global isobutylene volumes in future. Similar to isobutylene,
feedstock supply to light olefins production (a); ethylene, pro- 1-butene is generated by three quarters in FCC units. Only a
pylene, and butenes (b, c, and d). Own estimates were based on quarter of the global 1-butene volume is generated in ethylene
sources [1–6]. plants, mostly from naphtha and gas oil. Small volumes are
produced on purpose by dimerization of ethylene, e.g., by the
C4 olefin recovery in oil refineries, mainly from FCC units, Alphabutol process of the Institute Francais du Petrol (IFP).
and in small volumes in delayed coking units, directly yields These volumes are often used as co-monomer for the polyeth-
raffinate 1. These product streams can be further processed ylene (lldPE) production (Fig. 4).
jointly with similar streams from ethylene plants. The usual

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 crudes primary generation conversion processes products
Ethane / Ethylene Dimerisation
Propane
Natural Gas

Oxidative DeHydrogenation

Steam cracking
Butene-1
Butanes Crude C4
BD
[Butadiene-

Skeletal
Isomer.
SHU

N-butene Isom.
Condensate

Distillation
rich]

Catalytic
Raff III [butene-2-rich]
Raff II [butene-1-rich]
Methane (Hydro)-

Raff I [iso-butene-rich]
Isom.
Naphtha Higher Olefin

PIB
Cracking Butene-2
Crude Oil

Gas Oil
FCC Cracking

lation
Alky-
Alkylate
Vacuum gasoline
Delayed Coking

MTBE / TBA
Residue

cleavage
BD Isobutene

XTBE /
TAME
Acetylene Butanediol
Coal

Extract

Methanol-to-
Syn MeOH
Olefins
Gas
Bio mass

Full C4 Hydro
Butanes
Ethanol Ethanol- Iso-BDH n-BDH
to- Butadiene
Butadiene

Figure 2. Network of petrochemical and refinery processes for the generation and conversion of C4 hydrocarbons; Starting from raw ma-
terials a number of crudes are produced first that are used as feedstock for the primary generation of olefins. C4 olefins are further pro-
cessed from their raffinates and in some cases are recovered in substance before being used as a chemical feedstock.

Table 1. Composition of raw C4 hydrocarbon streams generated in different petrochemical and refinery processes; the red boxes indi-
cate the difference in butane to butene ratios between steam cracking and fluid catalytic cracking.

C4 Boiling Yield [wt %]

point [C]
SC, low SC, high FCC n-Butane Ethanol n-Butene MTO
severity severity cracker BDH ETB ODH [ZSM-5]

1,3-Butadiene –4.4 28 49 0.2 9–13 90 58 –

Isobutene –6.9 32 22 24 – – – ~ 30*

cis-Butene-2 +3.7 7 5 11 37–41 10 8 ~ 60

trans-Butene-2 +0.9 7 6 15

Butene-1 –6.3 20 14 15 – 1.3

Isobutane –11.7 2 1 37 – – – < 10**

n-Butane –0.5 4 3 12 ~ 50 – 4

Source [7] [7] [8] [9] [10] [11, 12]

Most of the 1-butene is consumed in the production of alky-
late gasoline, while only one quarter is used in the production
of chemicals and polymers. After isomerization to 2-butene
1-butene volumes are also consumed to produce propylene by
metathesis with ethylene. Similar to isobutylene volumes of
1-butene will grow mainly along with alkylate gasoline.The
supply and demand situation for 2-butene is very similar to
1-butene. 2-Butene is also produced mainly in refineries and is
converted by approx. three quarters into alkylate gasoline. The
FCC process yields a 2-butene to 1-butene ratio much closer to
thermodynamic equilibrium than that of the steam cracking
process. Thus, FCC units have a larger share in global 2-butene
production than in 1-butene production (Fig. 5).
Since most of the global C4 hydrocarbon volumes are pro-
duced in oil refineries this raises the question of why such a
small part of these volumes become available to the petrochem-
ical industry. As already explained above, C4 hydrocarbons in
refineries are mainly used as a feedstock for the gasoline pool,
either directly as a C4 additive in cooler periods of the year or
in warmer periods as alkylate gasoline or as tert-butyl ether

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 a) a)
Isobutane Propylene Methyl Ethyl
Dehydrogenation via metathesis Ketone,
14% 24% 6%

Steam cracking, Alkylate

liquid feed gasoline
b) 24% 70%
Fluid-catalytic
cracking, total Isobutylene by source 2-Butene by use
62% 30 Mmto / +4 % p.a. 14 Mmto / +4 % p.a.

b) b)
Synthetic Chemicals, Fluid-catalytic
Rubber other cracking, total
9% 3% 86%

MTBE / ETBE Steam cracking,

41% 14%

Alkylate
gasoline Isobutylene by use 2-Butene by source
47% 30 Mmto / +4 % p.a. 14 Mmto / +4 % p.a.

Figure 3. Global isobutylene volumes and growth; a) volumes Figure 5. Global butene-2 volumes and growth; a) volumes by
by production process, estimated from global capacities and production process, estimated from global capacities and typi-
typical C4 yields (see Fig. 1 and Tab. 1); b) volumes by use, esti- cal C4 yields (see Fig. 1 and Tab. 1); b) volumes by use, estimated
mated from [14–17]. from [20, 21].

a) Alkylate
gasoline
Ethylene 7%
dimerisation Butane
4% 7%
XTBE
2% Gasoline
Fluid-catalytic fractions
Bioethanol 75%
cracking, total
10%
73% Gasoline, total
Steam
∼1,000 Mmto / ∼1 % p.a.
cracking Butene-1 by source
23% 18 Mmto / +4 % p.a.
Figure 6. The global gasoline pool, volumes by component. In-
dividual components and their physical properties relevant to
b) gasoline blending are summarized in Tab. 2 [22, 23].
Chemicals Polybutene-1,
6% (XTBE, Fig. 6).When blending C4-based components in the
3%
gasoline pool, two main aspects are important: on the one
Polyethylene
(hdPE / lldPE) hand, blending alkylate gasoline and XTBE leads to an increase
9% of the octane number and, thus, of the gasoline quality; on the
Alkylate other hand, alkylate gasoline limits the so-called Reid vapor
gasoline pressure of gasoline more effectively than XTBE components.
73%
In difference, blending bioethanol into the gasoline pool leads
Propylene
Butene-1 by use to a significant increase of the Reid vapor pressure. This in-
via metathesis
10% 18 Mmto / +4 % p.a. crease can be compensated for by co-blending alkylate gasoline
better than by blending with XTBE components.
Figure 4. Global butene-1 volumes and growth; a) volumes by Consequently, the strong growth of bioethanol volumes in
production process, estimated from global capacities and typi- gasoline is, hence, coupled to an equally strong growth of the
cal C4 yields (see Fig. 1 and Tab. 1); b) volumes by use, estimated global alkylate gasoline demand. At the same time total gaso-
from [18, 19]. line production is almost stagnant, whereby available C4 hydro-

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Table 2. Individual components and their physical properties relevant to gaso- ponent for the gasoline pool, a trend still in its in-
line blending [22, 23] fancy. Biobutanol boosts the octane number of gas-
oline, but unlike bioethanol, without increasing its
Component Blend octane number Reid vapor pressure Net energy Reid vapor pressure. This would relieve the de-
(RON + MON)/2 [psi] [%]
mand for alkylate gasoline as a low-vapor pressure
Crude gasoline 88 6–11 100 blending component and, thus, could make C4 ole-
fins from refineries available for the petrochemical
Ethanol 112 18–22 65
industry.
Isobutanol 102 4–5 82 Since all three butenes are expected to grow by
about 4 % a–1, it will be interesting to see how the
Alkylate gasoline 95 4–5 95
corresponding volumes will be produced. With
C4 raffinate 86–104 50–70 ~ 105 much lower growth rates in gasoline volumes FCC
units will not be able to satisfy this growing demand
MTBE 110 8 80
alone. Also, with ethylene plants being converted
ETBE 111 4 83 from liquid to gas feedstock butene availability from
steam cracking will also decrease, potentially leaving
behind a supply gap in C4 olefins.
a)

3 Alternative Sources for Butenes

b)
Alkylate gasoline, total
∼65 Mmto / ∼4 % p.a.
Figure 7. Volumes and growth rates of the two main blend
components for the gasoline pool; a) bioethanol [24]; b) alkylate
gasoline [14].
carbon volumes, mostly from FCC units do not grow as
strongly as their two main gasoline products (Fig. 7).
No significant change of this situation can be expected mid-
term. Refinery operators will have only little incentives to ship
their C4 hydrocarbons to consumers in the petrochemical in-
dustry. Long term, the demand situation for alkylate gasoline
could ease, if bioethanol is substituted by biobutanol as a com-
When turning our view to alternative processes for manufac-
turing C4 olefins dehydrogenation of the corresponding butane
is the first process that must be mentioned. Iso- and n-butane
can be dehydrogenated to raffinate-2 and raffinate-1-compati-
ble product streams, respectively (Fig. 8). Butadiene-rich crude
C4 streams can be generated from n-butenes by oxidative dehy-
drogenation and can be further processed conventionally by
butadiene extraction. Butanes are available as feedstock in large
amounts from natural gas, from crude oil distillation, or as a
residual stream from raffinate processing in oil refineries and
petrochemical plants.
Industrial processes for dehydrogenation of light paraffins
are available from various licensors (Tab. 3). Due to thermody-
namics of the dehydrogenation reaction operating tempera-
tures are high at around 600 C and the processes are operated
at relatively low pressure. Most of the processes use a combina-
tion of platinum and tin as the active ingredient of the dehy-
drogenation catalyst while support materials are different for
different licensors. As an exemption the Catofin process uses
an alumina-supported chromium oxide catalyst.
Dehydrogenation processes typically operate at partial con-
version of the paraffin feedstock between 50 and 60 %. Under
these conditions the processes reach C4 olefin selectivities of
about 90 %. The remainder of the converted feedstock (~10 %)
forms coke deposits on the catalyst surface. These deposits are
used in some process types like in the Catofin and in the Ole-
flex process to generate internal process heat by combustion
during catalyst regeneration. In contrast, the STAR process uses
steam injection into the reactant stream to minimize coke de-
posits by internal steam reforming. Depending on the coke
management concept cycle times between two catalyst regener-
ation steps vary between a few minutes and several hours per
cycle for the various process types.

Figure 8. Dehydrogenation reaction of n-butane (left) and isobutane (right).

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Table 3. Industrial processes for the dehydrogenation of butanes to butenes [25–27].

Process parameters UOP oleflex Uhde STAR process Clariant Catofin Linde-BASF process

Reactor Moving bed, radial flow, Fixed-bed, isothermal plus adiabatic Fixed-bed, adiabatic Fixed-bed, isothermal
adiabatic reactor

T [C] 580–650 570–590 560–650 550–650

p [bar] 2 5 0.3–0.5 >1

Cycle time 5–10 d 7h 6–20 min ~9h

X(C4 ¢) per pass [%] 50 ~35 60–65 C3 ¢:30

S(C4 †) [%] n-C4 †: 81; > 91–93 90 C3 †:90

i-C4†: 91

Catalyst Pt-Sn on Al2O3 Pt-SN Zn/Ca aluminate Cr2O3 : Al2O3 Pt-Sn support

Endothermal dehydrogenation allows only partial conver- Adiabatic Isothermal Autothermal

sion of ethane, propane, and of butane feedstock in the techni-
high Tin Low Tin Low Tin
cally relevant range of operating temperatures up to 800 C
(Fig. 9). Heat of reaction can be introduced into the reaction ⋅
Q
volume in three different ways (Fig. 10): the reaction volume ⋅ ⋅ ⋅
can be heated externally, e.g., by gas burners. Alternatively, the Q Q Q
reactant gas flow can be preheated to temperatures high
enough above the kinetic onset temperature to carry heat into z, t
the reaction volume by its heat capacity. The heat capacity of
the reactant gas stream may be further increased by steam dilu- ΔRH = CP,gas ⋅ΔT ΔRH = ΔRHcomb. ΔRH = ΔRHcomb.
tion to increase the amount of heat introduced. Thirdly, heat of
preheated external gas H2 combustion
reaction can be generated internally by selective combustion of reactant gas firing in-situ
the hydrogen that is released by the dehydrogenation reaction.
Oxygen that is mixed into the reactant gas stream reacts with Figure 10. Heat management concepts for endothermal dehy-
the hydrogen on the dehydrogenation catalyst. drogenation processes; from [27].

and C4 dehydrogenation offer an incentive when compared to

100
Butane steam-cracking of these two paraffins.
Propane In contrast, steam cracking of ethane generates only small
75 volumes of low-valued light gas more comparable to light-gas
Ethane
yields in C3 and C4 dehydrogenation. Thus, the potential dehy-
Conversion [%]

drogenation of ethane would not offer the same incentive over

50
25
0 Catalytic cracking of methanol is an interesting way to produce
400 500 600
Temperature [°C]
Figure 9. Thermodynamically limited conversion of light para-
ffins in endothermal dehydrogenation. The gray area indicates
the catalytically relevant range of operating temperatures;
from: [27].
Variable economics of olefin-producing processes also de-
pend on by-product yields. As can be seen in Tab. 4 (yellow
boxes), when steam cracking propane and butanes, about one
quarter of the feedstock is converted into light gas, mainly syn-
thesis gas and methane. However, when dehydrogenating these
paraffins, the resulting light-gas yield is much lower. Hence, C3
ethane cracking as the dehydrogenation of higher paraffins
does over their respective steam cracking.
For the on-purpose production of butenes the dehydrogena-
tion of butanes is advantageous over all the other processes de-
scribed above, because it does not generate by-products in large
amounts.
700 light olefins in so-called ‘‘methanol-to’’ (MT) processes (Fig. 11).
2 CH3OH → CH3OCH3 + H2O → HCx + 2 H2O
Figure 11. Two-step reaction of methanol to hydrocarbons in
methanol-to processes.
The multitude of possibilities to produce methanol from car-
bon-containing raw materials via synthesis gas grants a flexible
access to light olefins from all four raw material sources – natu-
ral gas, crude oil, coal, and biomass.
While ExxonMobil’s original methanol-to-gasoline (MTG)
process was dedicated primarily to gasoline production from
methanol, later developments like UOP’s methanol-to-olefin

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Table 4. Industrial processes for the generation of light olefins and liquid hydrocarbons: product yields in percent of feedstock and
global volumes in Mmto [1–6, 28].

SC, C2 SC, C3 SC, C5 SC, naphtha SC, GOs Fuel-FCC Olefin-FCC n-Propane n-Butane
PDH

Load [Mmto feed] 80 28 19 ~ 250 35 570 30 10 10

Share of C2 † capacity [%] 28 7.5 4.1 53 5.7 1.3 4.0 – –

C2 † [Mmto] 42 11 6 ~ 80 9 ~2 ~6 – –

C2 † yield [%] 53 40 32 ~ 32 25 ~ 0.4 20 – –

C3 † [Mmto] 1 3.7 4 40 5 36 6 5 –

C3 † yield [%] 1.2 13.3 20 ~ 16 ~ 14 ~6 15–20 45 –

C4 † yield [%] 2.2 4 13 10 10 15 19 – 45

Liquids 1 5 8 ~ 22 ~ 36 ~ 55 ~ 35 – –

Co-crack 35 12 4–5 4 3 – – 50 50

Light gas ~8 25 23 ~ 16 ~ 11 3 9 5 5

(MTO) and Lurgi-Air Liquide’s methanol-to-propylene (MTP) er as can be seen from Fig. 12. Generating synthesis gas from
processes were aimed at producing light olefins (Tab. 5). How- coal requires more equipment than from natural gas due to ex-
ever, the main purpose of these processes is not the production tensive processing of solids.
of C4 olefins but mainly of propylene and ethylene. Rather, Depending on costs related to specific investment cheap coal
some modifications of these processes are available that further may not always be so cheap. The investment for a worldscale
upgrade the primary yield of the latter two olefins by catalytic
cracking of the small C4 olefins volumes that are co-generated
in the MT process. Industrial operating conditions allow for a
primary C4 hydrocarbon yield of ca. 10–12 %, most of it as C4
paraffins. Hence, an industrial MT process for producing C4
olefins is not readily available yet.

4 Economics of Olefin-producing
Processes
The cost structure of all MT processes depends indirectly on
the raw material that is used to produce the methanol feed-
stock. Coal is relatively cheap per gram of carbon that ends in
methanol compared to natural gas. However, its specific in- Figure 12. Economy of scale of petrochemical processes for the
vested capital per ton of methanol product is significantly high- production of light olefins based on alcohols as feedstock [33].

Table 5. Industrial processes for the catalytic cracking of methanol to hydrocarbons (MT processes).

ExxonMobil MTG UOP/HYDRO MTO Lurgi MTP Sinopec S-MTO

T [C] 400–420 340–540 425 350–550

p [bar] ~4 1–3 1.5 ~1

Catalyst ZSM-5 zeolite (ExxonMobil) SAPO-34 zeolite (UOP) ZSM-5 zeolite (Clariant) SAPO-34 zeolite (Chia Thai Energy Mat.)

S(C2) [%] 1.1 37 3 50–35

S(C3) [%] 4.5 37 64 30–45

S(C4) [%] C4 †: 1.1C4 ¢: 11.9 ~ 12 (lab:20–25) ~8 ~ 11

+
S(C5 ) [%] 82.3 (no C10+) ~7 ~ 25 < 10

Source [29] [30] [31] [32]

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MT plant based on coal may be higher by about $ 1.5 billion bution margin 1 (CM1). For the present paper CM1 was calcu-
than for one based on natural gas. For the first ten years, this lated based on published product yields for the various
investment penalty would result in higher costs of approx. processes and on U.S. market prices for feedstock and prod-
300 million $ a–1 (depreciation and capital costs at typical rates) ucts, respectively. All other cash expenses were neglected for
or around 150 $ t–1methanol. These added costs are higher than now. CM1 represents a rough estimate for the operating cash-
the variable cost advantage of coal versus cheap natural gas, flow and, thus, compares profitability between different pro-
i.e., at 4 $ MMBtu–1. Hence, under these conditions a coal- cesses.
based MT process will not be competitive versus one based on At current US market prices steam cracking of ethane yields
natural gas. However, when coal is cheap, i.e., at 60 $ t–1, and by far the highest CM1 margin, followed by propane dehydro-
natural gas is expensive, i.e., at 12 $ MMBtu–1, coal-based MT genation and by the two olefin-generating MT processes. CM1
processes become cost competitive (Fig. 13). margins of all other processes are significantly lower. For most
Economics of different petrochemical processes for the pro- of the processes CM1 margins are driven by the product mix,
duction of light olefins can be compared based on their contri- while for ethane cracking it is driven mainly by low feedstock
costs.
1,000
Regional differences, in general, play a major role in the se-
lection of suitable processes to produce light olefins and other
800 basic petrochemicals (Fig. 14). Differences in feedstock prices
US$ / metric ton

result from geological differences in raw material abundance.

600 In contrast, regional differences in market prices and product
demand result from differences in population and economic
400 power. Regions rich in raw material like the Middle East, the
former GUS countries, Australia, or Latin America possess a
200 comparatively small population and generate a low absolute
GDP. Petrochemicals that are produced in these regions are
0
predominantly exported, while countries poor in raw materials,
C3 Dehydro

MTP
C4 Dehydro
MTG
GO SC

Deep FCC

MTO

C2 Dimer.
Propane SC
Ethane SC

Naphtha SC

FCC
Butane SC

ETE

but rich in population and with a strong GDP like Europe or

Asia are net importers of these goods.
As an exception, the U.S. currently enjoy significant raw ma-
Figure 13. Economics of different petrochemical processes for terial resources and at the same time a strong demand for these
the production of light olefins; the values represent estimates of products in a large population with a strong economy. In addi-
contribution margins 1, i.e., revenue minus variable costs. All es- tion, U.S. petrochemical producers increasingly export their
timates are based on U.S. market prices for raw materials, feed- products globally.
stocks and products.

frmr. GUS states

Europe

North America

Asia Pacific
Middle East

Africa

Populaon

GDP
South America
Coal reserves
Australia
Oil reserves

Natural Gas reserves

Figure 14. Regional differences in population, GDP and raw material abundances; the global figures have been composed from individ-
ual Wikipedia entries by country for population, GDP and for the raw material reserves, respectively. Full scale of each graph represents a
60 % share of the region in the respective global figure.

www.ChemBioEngRev.de ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2014, 1, No. 4, 136–147 143
 Due to these regional differences it is necessary to take trans- a)
port costs for raw materials and for petrochemical products in-
to account when deciding on investments into petrochemical nitrile rubber Other
4% 4%
process equipment and on the location of the individual invest-
SBD block
ment (Tab. 6). copolymers
SB.
High specific costs are related to the transport of hydrocar- elastomers
6%
28%
bon equivalents in particular for liquefied natural gas (LNG)
and for liquefied petroleum gas (LPG). However, methanol and ABS polymers polybutadiene
biomass, such as corn, also come with relatively high transport 12% 26%
costs when calculated by the ton of hydrocarbon equivalent.
SB latex Butadiene
For LNG and LPG, costs are high mainly due to an extensive 10 Mmto / 4.5% p.a.
12%
infrastructure transport of methanol, and biomass is expensive
because they contain large amounts of water that must be
transported alongside. Due to cheap infrastructure, crude oil b)
and gasoline but also coal can be transported relatively cheap. Steam cracking,
Other (ODH)
The differences in specific transport costs require petro- Ethane & LPG
4%
chemical processes that are based on natural gas, ethane, and 17%
LPG to be operated in the region of raw material abundance,
FCC, total
e.g., in the Middle East, but also in the United States. Ethane
1%
cracking is currently big in these two regions. In contrast, oil-
or coal-based processes are often operated in the region where
petrochemical products are to be marketed, e.g., in Europe or Steam cracking,
in Asia. Olefin production in these two regions relies predomi- Naphtha & GO Butadiene
nantly on naphtha cracking and in Asia industrial MT plants 78% 10 Mmto / 4.5% p.a.
that use coal-based methanol feedstock have been installed
worldwide for the first time. Figure 15. Global butadiene volumes and growth; a) volumes
by production process; b) volumes by use; estimates based on
[39, 40].
5 Butadiene – A very special case
directions. These amplitudes are much larger than for the other
Butadiene represents a peculiar case in the world of C4 olefins. olefins, making decision timing for new investments into buta-
It is mainly used as a monomer in the production of various diene production very difficult.
elastomers. Elastomers are predominantly used in the tire in- At present butadiene is only produced by steam cracking of
dustry and, hence, its consumption pattern depends on the naphtha. Butadiene yields in FCC units are very low. Butadiene
global car industry. Its global volumes are somewhat smaller interferes negatively in the acid-catalyzed alkylate gasoline pro-
than for the other three C4 olefins, mostly because it is exclu- duction. Therefore, butadiene is removed from FCC raffinates
sively used in petrochemical production, while the other C4 by selective hydrogenation. With increasing amounts of ethane
olefins are consumed mainly in gasoline products (Fig. 15). cracking, butadiene may be produced in future by ethylene di-
Butadiene prices vary with large amplitudes over time merization followed by oxidative dehydrogenation.
(Fig. 16). Changes in demand and supply occur in sync over In addition to steam cracking butadiene could be produced
the economic cycle, leading to hefty price changes in both from coal or biomass via butanediol as an intermediate. Start-

Table 6. Overseas shipment costs for different raw materials and petrochemical products; cost figures have been collected from [34–38].

Commodity Shipment cost Energy content Shipment costs Shipment costs

[US $ t–1] [MMBtu t–1] [US $ MMBtu] [US $ t–1H2C eq.]

Liquefied natural gas (LNG) 140 53.4 2.64 160

Liquefied petroleum gas (LPG) 100 (Panama) 47.3 2.11–4.22 100–200

150–200 (Cape Horn)

U.S. crude oil 11–17 39.7 0.28–0.43 10–20

U.S. gasoline 10–12 41.2 0.41–0.49 10–12

U.S. coal 10–20 ~ 27 0.37–0.74 20–40 (via MTX)

U.S. methanol 30–60 19 1.58–3.16 70–140

U.S. ethanol 30–60 25.6 1.17–2.34 50–80

U.S. corn 30–60 ~ 15 2.00–4.00 109–174 (via EtOH)

www.ChemBioEngRev.de ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2014, 1, No. 4, 136–147 144
 5000 At butene conversion between 75 and 90 %, the selectivities
to butadiene range at 90 % or higher. Different mixed-metal
oxide catalysts are operated, resulting in space time yields be-
4000
Olefin prices tween 500 and 1000 kg m–3h–1. Feedstream compositions of the
2010-2013 different processes vary with regard to their content in oxygen,
steam, and butene.
US$ per ton

3000
CM1 margins for ODH processes are difficult to obtain due to
the large amplitudes in butadiene prices. For a representative
2000 butadiene price of 2000 $ t–1, the CM1 margin would amount to
approx. 400 $ t–1, when assuming typical U.S. prices for raffinate
feedstock. These estimates show that ODH processes will play
1000
an important role in the global butadiene supply in the future.

0
Figure 16. Prices for butadiene (red curve) versus those for eth-
ylene (blue), propylene (velvet), and naphtha (black) between
2010 and 2013; amplitudes in butadiene prices are much larger
than for the latter three materials [40].
ing with coal-based Reppe chemistry, butadiene could be ob-
tained by catalytic dehydration of butanediol, originally a pro-
cess that was operated in the 1940s to produce synthetic rub-
ber. A somewhat more conventional way to butadiene would
be the dimerization of ethanol [41] after Lebedev or after Os-
tromislensky. Bioethanol can be produced routinely from bio-
mass by fermentation. However, ethanol dimerization has not
been optimized for industrial yields. These processes were often
operated in war times or in isolated national economies. Hence,
their profitability is often not competitive in today’s world mar-
ket.
Beyond steam cracking of liquids, additional butadiene can
be generated by oxidative dehydrogenation (ODH) of n-bu-
tenes (Fig. 17).
O2, H2O
, , + H2O
6 Outlook – Biochemical Processes
for C4 Olefin Production
In the past, technical developments resulted in a number of fer-
mentative processes for the production of industrial chemicals.
With a 10% share in the global gasoline pool, bioethanol has al-
ready arrived in the group of very large industrial chemical
products. In recent years, several start-up companies have be-
gun to develop fermentation processes for the production of
higher industrial alcohols such as isobutanol and butanediol.
Typical yields of these processes range from 0.3 to 0.5 talcohol
per ton of sugar or corn starch [46] (Tab. 8).
Table 8. Fermentative yields of different industrial alcohols
(column 1 and 2, from: [46]) and CM1 margins of different ole-
fins obtained from these alcohols by catalytic dehydration (col-
umn 3 and 4). It is assumed for simplification that the dehydra-
tion process yields 100% olefins. *Prices [$ t–1]: 2000 (i-butylene)
and 2500 (butadiene).
Bio-alcohol Yield Olefin from CM1 [$ t–1]
bio-alcohol
Ethanol 0.45 t t–1corn Ethylene ~ 110

Isobutanol 0.35 t t–1sugar Isobutylene* –500 – +500

Figure 17. Oxidative dehydrogenation (ODH) of n-butenes to
butadiene. 1,4-Butanediol 0.5 t t–1sugar Butadiene* ~ 300

Product streams of these processes can be processed further Catalytic dehydration of the corresponding industrial mono-
similar to crude C4, i.e., by extraction of the butadiene. ODH alcohols easily yields ethylene [47] and isobutylene [48], while
processes were developed by several companies and some of the same reaction on 1,4-butanediol does not easily produce
these processes are available on a license basis (Tab. 7). butadiene [49] (Fig. 18).

Table 7. Survey of four different ODH processes; additional ODH processes were developed by BP Chemicals, Mitsubishi Chemicals and
Nippon Zeon.

Phillips O/X/D Petro/Tex Oxo/D SK Energy ODH BASF ODH

X (n-C4 †) [%] 75–80 75 83 ~ 95

S (BD) [%] 90 77.3 96 ~ 95

Steam: n-C4 †:O2 5–12:1:1 24:2:1 15:1>0.75 0–15:1:2

3 –1
STY (BD) [kg m h ] 24–780 550–1090 900 ~ 450

Catalyst Li-Sn-POx Zn-, Mn-, Mg-ferrite ZnFeFeO4 Bi-Mo-Fe-oxides

Source [42] [43] [44] [45]

www.ChemBioEngRev.de ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2014, 1, No. 4, 136–147 145
 7 Conclusion
Today, a number of processes for the gen-
eration, the conversion and the separa-
tion of C4 olefins in petrochemicals and
in oil refineries are already available on
industrial scale. At present the majority
of global C4 olefin volumes are generated
and further processed in oil refineries
making blend components for the gaso-
line pool. Their availability for petro-
Figure 18. Catalytic dehydration of various alcohols to the corresponding light olefins. chemical production purposes hinges on
their valuation relative to their alternative
production by petrochemical processes.
a) In future, butane dehydrogenation will yield increasing vol-
umes of C4 olefins. Smaller volumes of butadiene will be gener-
ated by oxidative dehydrogenation of butenes obtained by de-
hydrogenation before. MT processes may also be tuned for C4
olefin production depending on further process development.
Bio-based routes to C4 olefins are still in their infancy. Their
success will largely depend on the development of market pri-
ces for biomass raw materials and on a potential solution of the
conflict of food versus fuel.

The author has declared no conflict of interests.

Michael Bender received his

Ph.D. in Physical Chemistry in
b) 1997 from the Ruhr-Universi-
tät Bochum, having worked in
the group of Prof. Freund. He
took his first position with
BASF as catalyst researcher in
the same year. From 2001 to
2009, he held business posi-
tions with BASF as product
manager and business man-
ager for petrochemical cata-
lysts. In 2009, Dr. Bender be-
came a R&D group leader and
was promoted to Senior Expert in Catalyst Research with
Figure 19. Long-term market prices for sugar (a) [50] and for BASF SE, Ludwigshafen, in 2013.
maize (b) [51].

In any case, it can be concluded that the comparatively sim- References

ple dehydration of bio-based industrial alcohols can generate
positive CM1 margins and, depending on market prices, may [1]
become as profitable as conventional petrochemical processes. [2]
However, prices of bio-based raw materials for the fermenta-
tive production of alcohols may undergo drastic changes that [3]
could easily undermine process profitability on the long run.
After a long period of relatively stable prices soft commodities
have recently experienced price hikes that doubled or even
tripled market prices for certain carbohydrates (Fig. 19). [4]
Despite of these uncertainties additional efforts will be spent
in future developments of production processes for petrochem- [5]
icals on the basis of biomass can be expected. Hopefully, some
of these processes will also grant access to bio-based C4 olefins.
H. Zimmermann, Oil Gas Eur. Mag. 2009, 35 (4), 191.
R. Jawad, AIChE Meeting Saudi Arabian Section, Al-Khobar,
February 2007.
J. Jechura, Delayed Coking, CBEN409 Petroleum Refining
Processes lecture notes, Colorado School of Mines, Gol-
den, CO 2014. http://inside.mines.edu/~jjechura/Refining/
06_Delayed_Coking.pdf
Olefins via enhanced FCC, PERP Report 07/08S5, Nexant
Systems, San Francisco, CA 2009.
J. Gregor, D. Wie, in Handbook of Petroleum Refining Pro-
cesses, (Ed: R. A. Meyers), 3rd ed., McGraw-Hill, New York
2004.

www.ChemBioEngRev.de ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2014, 1, No. 4, 136–147 146
 [6] Refinery Fluid Catalytic Cracking Units – Global Market
Analysis, Capacity Forecasts and Competitive Landscape to
2016, Report, Global Data, London 2011.
[7] K. Weissermel, H.-J. Arpe, Industrielle Organische Chemie,
4th ed., VCH-Verlag, Weinheim 1994.
[8] Chemical Technology (Organic), Module VII, National Pro-
gramme on Technology Enhanced Learning (NPTEL),
Chennai 2014.
[9] C. A. Arvind, K. R. Prakash Rao, K. S. Suryanarayanan, B.Sc.
Thesis, Anna University, Chennai 2005.
[10] a) W. J. Toussaint, J. T. Dunn, D. R. Jachson, Ind. Eng. Chem.
1947, 39 (2), 120; b) W. J. Toussaint, J. Lee Marsh, Synthetic
Rubber (Eds: G. S. Whitby, C. C. Davis, R. F. Dunbrook),
John Wiley and Sons, New York 1954, 86.
[11] D. McCann, D. Lesthaeghe, P. W. Kletnieks, D. R. Guenther,
M. J. Hayman, V. Van Speybroeck, M. Waroquier, J. F. Haw,
Angew. Chem. 2008, 120 (28), 5257.
[12] G. F. Froment, W. J. H. Dehertog, A. J. Marchi, Catalysis,
Vol. 9, (Ed: J. J. Spivey), RSC Publishing, London 1992, 1.
[13] a) J. Houžvička, V. Ponec, Catal. Rev. 1997, 39 (4), 319;
b) W. E. Evans, S. C. Stem, US Patent 4 804 802, 1989;
c) S. C. Stem, W. E. Evans, US Patent 4 855 529, 1989;
d) J. Barin Wise, D. Powers, AIChE Annual Meeting, St.
Louis, MI, November 1993.
[14] P.S. Pryor, Petrol. Technol. Quarterly Winter 2004 (2004), 69.
[15] Methyl Tertiary Butyl Ether (MTBE) Global Markets to 2020
– China Dominates Global MTBE Demand While Developed
Regions Look to ETBE and Ethanol as Replacement Options,
Report GBICH0067MR, GBI Research, New York 2012.
[16] B. N. M. van Leeuwen, A. M. van der Wulp, I. Duijnstee,
A. J. A. van Maris, A. J. J. Straathof, Appl. Microbiol. Biotech-
nol. 2012, 93, 1377.
[17] K. Nagai, T. Ui, Trends and Future of Monomer-MMA Tech-
nologies, R&D Report, vol. 2004-II, Sumitomo Chemical,
Tokyo 2004.
[18] R. J. Gartside, M. I. Greene, H. Kaleem, Hydrocarbon Process.
2006, April, 57.
[19] a) A. Forestière, H. Olivier-Bourbigou, L. Saussine, Oil Gas
Sci. Technol. 2009, 64 (6), 649–667; b) F. Favre, A. Forestière,
F. Hugues, H. Olivier-Bourbigou, J. A. Chodorge, Oil Gas
Eur. Mag. 2005, (2), 83.
[20] J. M. Hildreth, Hydrocarbon Eng. 2013, 18 (2), 23.
[21] a) Product Safety Summary for Methyl Ethyl Ketone, Exxon-
Mobil, Irving, TX, January 2014; b) pubchem.ncbi.nlm.nih.
gov/toc/summary_toc.cgi?tocid=321&cid=6569
[22] OPEC World Oil Outlook 2013, Organization of the Petrole-
um Exporting Countries, Vienna 2013.
[23] P. Aakko-Saksa, P. Koponen, J. Kihlman, M. Reinikainen,
E. Skyttä, L. Rantanen-Kolehmainen, A. Engman, VTT
Working Papers No. 187, VTT Technical Research Centre of
Finland, December 2011.
[24] World Biofuels Report, F. O. Licht, London 2011.
[25] Catalysis, Vol. 11 (Eds: S. K. Agarwal, J. J. Spivey), RSC Pub-
lishing, Cambridge, 1994.
[26] S. Airaksinen, Ph.D. Thesis, Helsinki University 2005.
[27] M. Dieterle, 47th Annual Meeting of the German Catalytic
Society (47. Deutsche Katalytikertagung), Weimar, March
2014.
www.ChemBioEngRev.de ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[28] S. I. Kantorowicz, 2nd Asian Petrochemical Technology Conf.,
Seoul, May 2002.
[29] a) X. Zhao, R. D. McGihon, S. A. Tabak, ExxonMobil,
Hydrocarbon Eng. 2008, 13 (9), 39; b) R. F. Probstein, R. E.
Hicks, Synthetic Fuels, McGraw-Hill, New York, 1982.
[30] G. A. Funk, D. Myers, B. Vora, Hydrocarbon Eng. 2013, 18
(12), 25.
[31] W. Liebner, Progress report from s/u of Lurgi’s MTPs in China,
Lurgi GmbH, Frankfurt/Main, October 2010.
[32] L. Hongxing et al., German Society for Petroleum and Coal
Science and Technology (DGMK) Conference, Dresden,
October 2013.
[33] M. E. Jones, 21st Ethylene Producers’ Conference, Tampa, FL,
April 2009.
[34] http://www.petrostrategies.org/Learning_Center/
oil_transportation.htm#Shipping (accessed on June 22, 2014)
[35] http://www.envisionfreight.com/value/pdf/Grain.pdf (ac-
cessed on June 20, 2014 )
[36] K. Grover, 16th IMPCA Asian Methanol Conference, Singa-
pore, November 2013.
[37] D. Mavrinac, LNG & LPG Shipping Fundamentals, Jefferies
LLC, New York 2013.
[38] Ocean Freight Rates for Coal, Coal Age, http://
www.coalage.com/features/3230-ocean-freight-rates-for-
coal.html (accessed on December17, 2013)
[39] B. G. Sampat, Chemical Weekly 2010, August 24, 203.
[40] B. Bekaert, 20th Asian Petrochemical Summit, Singapore,
September 2013.
[41] B. B. Corson, H. E. Jones, C. E. Welling, J. A. Hinckley, E. E.
Stahly, Ind. Eng. Chem. 1950, 42 (2), 359.
[42] P. C. Husen, K. R. Deel, W. D. Peters, Oil Gas J. 1971, 16
(31), 60.
[43] L. Marshall Welch, L. J. Croce, H. F. Christmann, Hydro-
carbon Process 1978, 57 (11), 131.
[44] H. Lee, J. C. Jung, H. Kim, Y.-M. Chung, T. J. Kim, S. J. Lee,
S.-H. Oh, Y. S. Kim, I. K. Song, Catal. Lett. 2009, 131, 344.
[45] a) K. Harth, H. Hibst, G.-P. Schindler, C. Walsdorff, WO Pat-
ent 2004/007408 A1, 2004; b) C. Klanner, G.-P. Schindler,
S. Crone, F. Borgmeier, M. Duda, F. Simon, WO Patent
2006/075025, 2006.
[46] a) A. J. J. Straathof, Chem. Rev. 2014, 114 (3), 1871; b) R. Ko-
lodziej, J. Scheib, Hydrocarbon Process. 2012, 9, 79; c) E. M.
Green, Curr. Opin. Biotechnol. 2011, 22, 1; d) M. J. Burk, Int.
Sugar J. 2010, 112 (1333), 30.
[47] A. Morschbacker, Polym. Rev. 2009, 49 (2), 79.
[48] P. A. Armstrong, B. Bhatt, E. C. Heydorn, B. A. Toseland, US
DOE Coal Liquefaction and Gas Conversion Contractors
Review Meeting, Pittsburg, PA, September 1993.
[49] a) A. Igarashi, S. Sato, R. Takahashi, T. Sodesawa, M. Ko-
bune, Catal. Commun. 2007, 8, 807; b) H. Inoue, S. Sato,
R. Takahashi, Y. Izawa, H. Ohno, K. Takahashi, Appl. Catal.,
A 2009, 352, 66.
[50] http://blogs.lawrence.edu/economics/2012/02/cant-beet-
these-profit-margins.html (accessed on June 20, 2014).
[51] http://chinaag.org/prices/international-prices/grain-prices-
global/ (accessed on June 20, 2014).
ChemBioEng Rev 2014, 1, No. 4, 136–147 147